Esters of polyglycerol



'ottheseacidsf 'The poly lyceroh which is reacted with the so acids, is prepared by'heating glycerolat an ele- Patented May 26, 1942v UNITED STATES PATENT .orrlcs i 2,284,127 g v V r Herman A. Bruson, P

to Biihm & HaasOo No Drawing-1 A Serial No.'339,330

I l parry, Philadelphia, Pa.

on sine "1, 1940,

- elphia, Pa; assignor sclaims. ((1260-5410) This invention relates to new compositions of matter which are eilfective as emulsifying. wetting, and dispersing agents. The new compositions are also efiective as insecticides, asdisclosed in my .copending application Serial No.

259,317 filed March 2, 1939, of which the present application represents a continuation-in-part.

The object of this invention is to provide oilsoluble wetting, dispersing, and emulsifying agents. It is also an object to provide such agents which are compatible and useful in conjunction with other wetting, dispersing; and

atmosphere until there has been a weight loss of 25 to 30%. The viscosity of a 75% solution. of the polyglycerol prepared in this way usually corresponds to D on the Gardner-Holdt scale.

In preparing the-wetting; dispersing,and emulsifying composition from the above materials the pclyglycerol, the monoba'sic aliphatic or cyemulsifying agents, 'improving the value of the latter agents, and overcoming their incidental deficiencies, such as imparting low viscosities, causing drain-01f of solutions, etc.

The new compositions of matter are in general thick, balsam-like materials obtained by reacting other hand, be dissolved in oils or oily materials .and used in this form or in the form of emulsions.

The monobasic, aliphatic acids-which are useful in this inventionbontain, from. eight carbon atoms upward. 'YThey may contain a chain interrupted by :oxygen;" }'1fypicaljacids include caproxyacetic capryLphenoxyac'etic acid, un-

decylenic acid,.9 pry11c. acid, lauric acid, palmitio cloaliphatio acid, and the resin-forming acid are mixed and heated, under an inert atmosphere until the acid number ofthe resulting product 'is reduced to a low value, preferably below 15,

and the viscosity is about B to D on the Gardner-Holdt scale. Temperatures between 180C. to 240 C. are used to effect the reaction, the temperature chosen depending upon the par- 3 ticular combination of materials, the exact nature' of the product desired, and its intended use. The products obtained are thick and syrupy at ordinary temperatures, although they usually solidify in the cold. The products-are nonresinous. Films of the product are-oily and somewhat tacky but are non-drying. The products are dispersible or soluble in water, oils, and various organic solvents. In the preferred compositions about twice as much of themonobasic aliphatic or cycloaliphatic acid is taken as of polyglycerol. These acids in general constitute about'45% toabout 75% of the total materials reacted with the polyglycerolconstituting-40% to 20%. The amount of resin-forming dicarboxylic acid which can be used does not exceed- 15% of the materials and acid, ricinolic' -ac id leic' acid, stearic'acid, etc.

Pure acids be "used-for "commercially' available acids obtainable, from'non-drying. oils, such as cocoanut j. oil, .btton'sed oil,' etc. The cycloaliphatic acids react much like the allphatic acids, most important being naphthenic acidsf 'trom petrpleumfgin individual aliphatic acid at waif-type '1 prescribed, or cycloaliphatic acid, ormixturesthereof may beused as a starting material.

a The resin-forming dicarboxylic acidsz,which have proved to 'be of, .value include'phthalic, succinic, maleic, an'd sebacicacids mixtures vated temperature in the presence of ajlittle may be as low as 3%. The exact proportions of I the various starting materials which are reacted depend upon the particular materials selected. The proportions must be so selected and adjusted that a homogeneous, non-drying material results. If larger amounts of a dicarboxylic acid is used than indicated, there is danger of the separation into aresinous mass and an oily layer of little value. Also, the proportions must be so selected that a low acid number is reached without over long heating of the reacting materials, for with alkali. In the preferred procedure; about 1% or c potassium hydroxide is added to glycerine which is stirred and heated at 250-260 C .',in'an inert 55 excessive times of heating or excessive tempera- 5 'tur'es the acid number may at first decrease and then increase.

When the compositions are to be used as insecticides or in parasiticidal mixtures the acid number, as determined by the usual methods usedin varnish and resin making must be low,

forliree ratt'y' acid, has been found injurious to- ,pianta'--' .When the acid number is between 15 and 5, the reaction product may be applied alone or igficoniunction with other Spray materials with t danger'to the more resistant plants and ily in water.

only slight m to the most sensitive. when the acid numberis less than 5 the reaction product can be applied at relatively high concentrations without fear of inJuryto even delicate plants. A low acid number has also been found highly desirable, in factsometimes essential, in other applications than the insecticidal. In the dispersion of dyes, lakes, and pigments, material of -low acid number often gives the optimum resultsi For various emulsions compositions essentially free, from acid have also been found advan-' 'tageous.

Details of the preferred process of reacting polyglycerol monobasic acid and resin-forming,

' dlcarboxylic acid are given in the following extained at this temperature until the acid number of the mass-had fallen below five. This required six and one-half hours. During this time a current of carbon dioxide gas kept an inert atmoscompositions to wet and film metal surfaces. They are advantageous in such applications since they are free from the active anions of the usual wetting agents, such as chloride or sulfate. In some of the anti-corrosive compositions the compositions of this invention serve to displace droplets of water which might otherwise remain and such as softening and conditioning yarns and fabrics of silk, wool, rayon, linen', cotton, etc.,'

and may be used as emulsifying agent and softener in spinning and throwing oils. They form a useful ingredient in cutting and grinding compounds.- They are useful in dispersing dyes, lakes,

phere above the reacting materials. 'Stirring.

was continuous and eflicient. The product was thick and oily in appearance, but dispersed read- It was miscible with thiocyanic acid esters, oils, hydrocarbon extracts of common insecticidal principles, etc. a

. In place of the undecylenic acid, there was used the fatty acidobtained from cocoanut oil. The reaction was .carried on for about sixhours, at which time the acid number was between two and three. This product was likewise thick and appeared oily. It was easily dispersible in water and miscible with other liquid organic insecticides.

Example '2.-200 parts of naphthenic; acid (average molecular weight 190) was combined in an open kettle with 100 parts of polyglycerol (viscosity D by the Gardner-Holdt scale, when in 75% aqueous solution) andv with parts of phthalic anhydride. The temperature of the mass was kept at 200 C. until the acid number was 2.8. As before, emcient stirring and an inert atmosphere were used. The product was a viscous syrup which was water-dispersible and miscible with oils. i

Emmple 3.Glycerol was heated at 250 C. with 1% sodium hydroxide until a 75% solution of the product showed a viscosity at C. of about D on the Gardner-Holdt scale. 100 parts of this polyglycerol, 200 parts of sec. octyloxyacetic acid, CeHn-O-CHs-COOH, and 20partsof phthalic anhydride were heated together at about 200C. until the acid, number of the product was less than three. This required three hours.- As before, eificient stirring and an inert'atmosphere were used. The product was a thick, oily material which .was water-dispersible and miscible with oils, liquid organic insecticides, etc.

toners, and pigments for use n l' ting pastes, printing inks, paints, enamels, lacquers, etc.

Their value as combined insecticidal, emulsifying.

wetting, and sticking agents in parasiticidal compositions has already been discussed in detail in application Serial No. 259,317, filed March 2,

I claim:

1. As a new composition of matter the substantially neutral, water-dispersible, non-resinous reaction product of 3 to 15 parts of a resinforming, carboxylic acid, 20 to 40 parts of polygly rol, and to parts of an acid se lected from the group consisting of monobasic aliphatic'acids which are not of the drying W and which possess at least eight carbon atoms,

.20 to 40 parts of polyglycerol, and 45 to as parts of an acid selected from the group consisting of monobasic. aliphatic acids which are not of the 'drying type and which possess at least eight carchain interrupted by an oxygen atom, cycloaliphatic acids, and mixtures of'these acids, said reaction product an acid 'number'less fifteen. I 3. As 'anewco'mposition of matter the substantially neutral, water-dispersible, non-resine ous reaction product of 3 to15 partsof a resinforming dicarboxylic acid,.20 to 40 of polybonatoms.

. The compositions described are valuable wetting, dispersing, and compositions finding a wide variety of applications alone and in conjunction" withother wetting agents and 4. As anew composition of matter the substantiallyneutral, water-dispersible, non-resinous reaction product of 3 to 15 mm of phthaiic acid. 20 to 40 parts of polyglycerohand 45to 7 5 1 parts of a monobasic, non-drying aliphatic acid having at least eight carbon atoms.

'5. As a newcomposition of matterthe substantially neutral, water-dispersible, non-resinous reaction product of; to 15 parts of-phthalic anhydride, 20 to 40 parts of 'mml, and 45, 

